CN104226358A - Method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation and catalytic reaction system - Google Patents
Method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation and catalytic reaction system Download PDFInfo
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- CN104226358A CN104226358A CN201410351466.6A CN201410351466A CN104226358A CN 104226358 A CN104226358 A CN 104226358A CN 201410351466 A CN201410351466 A CN 201410351466A CN 104226358 A CN104226358 A CN 104226358A
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- phenolic compound
- nickel formate
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Abstract
The invention provides a method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation. The method is performed in a high-pressure reactor, the phenol compounds serve as raw materials, and alkane solvents are adopted. The method is characterized in that a catalytic reaction system consisting of nickel formate and solid acids is used, metal Ni generated by in-situ decomposition of nickel formate serves as an active ingredient for hydrogenation, and hydrogen generated by decomposition of nickel formate can provide a high-activity hydrogenation hydrogen source. The invention also provides a catalytic reaction system used in a hydrodeoxygenation reaction for catalyzing the phenol compounds. The raw materials used in the catalytic reaction system provided by the invention are readily available, low in price, easy to operate and high in reaction activity. In activity evaluation of the catalytic system, the conversion rate of each phenol compound is close to 100 percent.
Description
Technical field
The invention provides method and catalystic converter system that a kind of phenolic compound catalytic hydrodeoxygenation prepares alkane, particularly a kind of method and catalystic converter system utilizing original position metallic nickel coupling solid acid to act on the reaction of catalysis phenolic compound hydrogenation deoxidation.
Technical background
Lignin, as the chief component of living beings, is the Main By product of lignocellulose biomass by hydrolyzation fermentation ethanol industry and paper industry, owing to being not fully utilized, becomes environmental contaminants, brings very large pressure to environment.Lignin is a kind of natural polymers be made up of phenylpropyl alcohol alkyl structure unit, can realize liquefaction, obtain product liquid by the degraded of catalysis orientation.But containing a large amount of phenols oxygenatedchemicals in product liquid, the performance indications such as its calorific value, viscosity, stability and corrosivity can not meet the needs of using energy source terminal client, therefore, it is necessary for carrying out efficient catalytic hydrogenation deoxidation PROCESS FOR TREATMENT (HDO) to the phenolic product of liquefying lignin.
Prior art bibliographical information is by sulfuration NiMo, CoMo catalyst application of being carried on the carriers such as aluminium oxide, active carbon, silica, alumina silicate in the hydrogenation deoxidation technique of bio oil, and part realizes the lifting of bio oil performance indications.As patent application WO-2007/141293 describes a kind of hydrodeoxygenation process being derived from the raw material of renewable source, it uses and is selected from containing at least one the catalyst being in sulphided form that the metal of VIII bunch and at least one are selected from the metal of VIB bunch, and the mol ratio of one or more metals being wherein selected from VIII bunch and one or more metals being selected from VIB bunch is in the scope of 0.48-0.97.But this process must introduce sulfur-containing compound (as H in catalystic converter system
2s, thiophene phenol etc.) to have stablized the metal sulfuration phase of catalytic action.In without the bio oil of sulphur, introduce sulfur-containing compound pollution sources, be a shortcoming of this technique.For overcoming this shortcoming, scientific worker starts to explore the noble metal hydrogenation dehydrogenation catalyst with high catalytic activity, and as the catalyst such as Rh, Pt, Pd of solid acid support type, or noble metal is coupled with inorganic acid the HDO catalystic converter system formed.But due in hydrogenation deoxidation process, oxygenatedchemicals is easily polymerized, coking, catalyst is not long for service life, and noble metal price is high in addition, inhibits the large-scale application of such catalyst to a certain extent.
Summary of the invention
The object of this invention is to provide a kind of method being applied to phenolic compound hydrogenation deoxidation and preparing hydrocarbon compound, and the catalystic converter system used in the reaction.
To achieve these goals, this invention takes following technical scheme:
Catalysis phenolic compound hydrogenation deoxidation of the present invention prepares the method for hydrocarbon product, carry out in autoclave, take phenolic compound as raw material, adopt alkane solvents, it is characterized in that: the method uses the catalystic converter system be made up of nickel formate, solid acid, the W metal that nickel formate decomposition in situ produces is hydrogenation active component, and nickel formate decomposes the hydrogen produced can provide highly active hydrogenation hydrogen source.
Described solid acid is selected from HZSM-5, Nb
2o
5, SiO
2-ZrO
2.
Described alkane solvent is selected from normal octane, n-dodecane, hexadecane, cyclohexane, decahydronaphthalene.
In described catalystic converter system, the consumption of nickel formate is between the quality 12.1% ~ 41.3% of phenolic compound.
In described catalystic converter system, the mass ratio of nickel formate and solid acid is between 1:0.2 ~ 2.
Nickel formate in described catalystic converter system and solid acid directly add in reaction system.
The reaction temperature of described catalystic converter system controls between 270 ~ 340 DEG C.
The initial H of reaction of described catalystic converter system
2stress control is between 2 ~ 5MPa.
In described catalystic converter system, phenolic compound and solvent quality are than between 1:1 ~ 1:100.
Present invention also offers a kind of catalystic converter system used in the reaction of catalysis phenolic compound hydrogenation deoxidation, it is characterized in that being made up of nickel formate and solid acid, nickel formate and solid acid directly add in reaction system, nickel formate is the presoma of hydrogenation active metals, be coupled with solid acid the catalystic converter system forming and have hydrogenation and deoxidation dual-use function, and wherein solid acid is selected from HZSM-5, Nb
2o
5, SiO
2-ZrO
2, the mass ratio of nickel formate and solid acid is between 1:0.2 ~ 1:2, and the W metal that nickel formate decomposition in situ produces is hydrogenation active component, and nickel formate decomposes the hydrogen produced can provide highly active hydrogenation hydrogen source.
The present invention with phenolic compound (with phenol, guaiacol, vanillic aldehyde, eugenol, anethene, ortho-methyl phenol and 2,4-xylenols etc. are representative) to prepare alkane be target to hydrogenation deoxidation, formic acid nickel is the presoma of hydrogenation active metals, with HZSM-5, Nb cheap and easy to get
2o
5, SiO
2-ZrO
2solid acid coupling composition has the catalystic converter system of hydrogenation and deoxidation dual-use function.In catalytic hydrodeoxygenation reaction system involved in the present invention, the W metal that nickel formate decomposition in situ produces is hydrogenation active component, and nickel formate decomposes the hydrogen produced can provide highly active hydrogenation hydrogen source; Solid acid then can realize phenolic compound molecule absorption and activation, go the functions such as hydroxyls dehydrate, and be coupled with hydrogenation reaction and realize the hydrogenation deoxidation of phenolic compound.In addition, relative to support type bifunctional catalyst, in catalyst system and catalyzing of the present invention, hydrogenation active metals and functional solid acid vectors almost do not interact, and breach the surface two dimension constraint of solid carrier, hydrogenation active metals shows better catalytic activity; Active metal can not the acid active sites of covering catalyst carrier, and the hydroxyls dehydrate that goes be conducive in the adsorption activation of phenolic compound and course of reaction reacts.
The W metal that the present invention is produced by nickel formate decomposition in situ and HZSM-5, Nb
2o
5, SiO
2-ZrO
2solid acid coupling forms hydrogenation deoxidation catalystic converter system, realizes phenolic compound through the conversion of hydrogenation deoxidation to hydrocarbon compound.In the present invention, raw materials used price is comparatively cheap is easy to get, and using method is simple, and reactivity is high.In the catalytically active assessment of catalyst system and catalyzing, the conversion ratio of most of phenolic compound is close to 100%.
Specific implementation method
To the present invention be further illustrated in the examples below, but the present invention will not be construed as limiting.
The catalystic converter system used in the reaction of catalysis phenolic compound hydrogenation deoxidation that the invention provides, be made up of nickel formate and solid acid, nickel formate and solid acid directly add in reaction system, nickel formate is the presoma of hydrogenation active metals, be coupled with solid acid the catalystic converter system forming and have hydrogenation and deoxidation dual-use function, and wherein solid acid is selected from HZSM-5, Nb
2o
5, SiO
2-ZrO
2, the mass ratio of nickel formate and solid acid is between 1:0.2 ~ 1:2, and the W metal that nickel formate decomposition in situ produces is hydrogenation active component, and nickel formate decomposes the hydrogen produced can provide highly active hydrogenation hydrogen source.
The reaction that catalysis phenolic compound hydrogenation deoxidation prepares alkane is carried out in HV XLPE power cables reactor, take phenolic compound as raw material, adopts alkane solvents, adds the catalyst system be made up of nickel formate and solid acid and carry out stirring reaction.The reaction time of all embodiments is all set as 5h, and mixing speed is 800rmp.
The reaction condition of each embodiment, phenols reactant species and reaction result are all listed in table 1.
Table 1
Conversion ratio computing formula is:
Claims (9)
1. a catalysis phenolic compound hydrogenation deoxidation prepares the method for hydrocarbon product, carry out in autoclave, take phenolic compound as raw material, adopt alkane solvents, it is characterized in that: the method uses the catalystic converter system be made up of nickel formate, solid acid, the W metal produced with nickel formate decomposition in situ is for hydrogenation active component, and nickel formate decomposes the hydrogen produced provides hydrogenation hydrogen source.
2. catalysis phenolic compound hydrogenation deoxidation as claimed in claim 1 prepares the method for hydrocarbon product, it is characterized in that described solid acid is selected from HZSM-5, Nb
2o
5, SiO
2-ZrO
2.
3. catalysis phenolic compound hydrogenation deoxidation as claimed in claim 1 prepares the method for hydrocarbon product, it is characterized in that described alkane solvent is selected from normal octane, n-dodecane, hexadecane, cyclohexane, decahydronaphthalene.
4. catalysis phenolic compound hydrogenation deoxidation as claimed in claim 1 prepares the method for hydrocarbon product, it is characterized in that: in described catalystic converter system the consumption of nickel formate be phenolic compound quality 12.1% ~ 41.3% between.
5. catalysis phenolic compound hydrogenation deoxidation as claimed in claim 1 prepares the method for hydrocarbon product, and its feature comprises: the mass ratio of nickel formate and solid acid is between 1:0.2 ~ 1:2.
6. catalysis phenolic compound hydrogenation deoxidation as claimed in claim 1 prepares the method for hydrocarbon product, it is characterized in that: reaction temperature is between 270 ~ 340 DEG C.
7. catalysis phenolic compound hydrogenation deoxidation as claimed in claim 1 prepares the method for hydrocarbon product, it is characterized in that: react initial H
2pressure is between 2 ~ 5MPa.
8. catalysis phenolic compound hydrogenation deoxidation as claimed in claim 1 prepares the method for hydrocarbon product, it is characterized in that: phenolic compound and solvent quality are than between 1:1 ~ 1:100.
9. the catalystic converter system used in the reaction of catalysis phenolic compound hydrogenation deoxidation, it is characterized in that being made up of nickel formate and solid acid, nickel formate and solid acid directly add in reaction system, nickel formate is the presoma of hydrogenation active metals, be coupled with solid acid the catalystic converter system forming and have hydrogenation and deoxidation dual-use function, and wherein solid acid is selected from HZSM-5, Nb
2o
5, SiO
2-ZrO
2, the mass ratio of nickel formate and solid acid is between 1:0.2 ~ 1:2, and the W metal that nickel formate decomposition in situ produces is hydrogenation active component, and nickel formate decomposes the hydrogen produced can provide highly active hydrogenation hydrogen source.
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|---|---|---|---|
| CN201410351466.6A CN104226358B (en) | 2014-07-22 | 2014-07-22 | Method for preparing alkane by catalyzing phenol compounds through hydrodeoxygenation and catalytic reaction system |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104862023A (en) * | 2015-05-19 | 2015-08-26 | 中国科学院广州能源研究所 | Method for producing biomass gas through chemical catalysis |
| CN113385204A (en) * | 2021-06-21 | 2021-09-14 | 复旦大学 | Nickel-based metal phosphate catalyst and preparation method and application thereof |
| CN113663682A (en) * | 2021-07-12 | 2021-11-19 | 西南林业大学 | Non-supported mesoporous hydrodeoxygenation catalyst and preparation and application thereof |
| CN115364867A (en) * | 2021-05-18 | 2022-11-22 | 南京林业大学 | Preparation of bimetallic catalyst and method for applying bimetallic catalyst in catalytic hydrogenation of guaiacol and other phenolic model compounds |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104862023A (en) * | 2015-05-19 | 2015-08-26 | 中国科学院广州能源研究所 | Method for producing biomass gas through chemical catalysis |
| CN104862023B (en) * | 2015-05-19 | 2017-11-21 | 中国科学院广州能源研究所 | A kind of method of chemical catalysis production biological fuel gas |
| CN115364867A (en) * | 2021-05-18 | 2022-11-22 | 南京林业大学 | Preparation of bimetallic catalyst and method for applying bimetallic catalyst in catalytic hydrogenation of guaiacol and other phenolic model compounds |
| CN113385204A (en) * | 2021-06-21 | 2021-09-14 | 复旦大学 | Nickel-based metal phosphate catalyst and preparation method and application thereof |
| CN113663682A (en) * | 2021-07-12 | 2021-11-19 | 西南林业大学 | Non-supported mesoporous hydrodeoxygenation catalyst and preparation and application thereof |
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| CN104226358B (en) | 2017-01-25 |
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